A. Introduction
Molecular sieves are a commercially important class of crystalline materials. They have distinct crystal structures with ordered pore structures which are demonstrated by distinct X-ray diffraction patterns. The crystal structure defines cavities and pores which are characteristic of the different species. Natural and synthetic crystalline molecular sieves are useful as catalysts and adsorbents. The adsorptive and catalytic properties of each molecular sieve are determined in part by the dimensions of its pores and cavities. Thus, the utility of a particular molecular sieve in a particular application depends at least partly on its crystal structure. Because of their unique sieving characteristics, as well as their catalytic properties, molecular sieves are especially useful in such applications as gas drying and separation and hydrocarbon conversion. The term "molecular sieve" refers to a material prepared according to the present invention as a fixed, open-network structure, usually crystalline, that may be used to separate hydrocarbons or other mixtures by selective occlusion of one or more of the constituents, or may be used as a catalyst in a catalytic conversion process.
B. Problems with Use of Templates
Prior art methods of preparing crystalline zeolites require a structure-directing agent or template (see, e.g., U.S. Pat. Nos. 4,076,842; 4,296,083 and 4,490,342, regarding Zeolite ZSM-23 and U.S. Pat. No. 5,053,373, regarding Zeolite SSZ-32). Such templates add to the expense and complexity of the process. Templates are typically relatively expensive organic compounds and thus increase the expense of reactants for the process. After crystallization of the zeolites, it is necessary to remove the templates from the interior of the crystals since they would otherwise block the pores. This is accomplished by heating and thus adds additional processing complexity and expense to the process. There are also environmental risks associated with the use of the organic templates.
C. Problems with Excess Water in Reaction Mixtures
Prior art methods of preparing crystalline zeolites typically produce finely divided crystals which must be separated from an excess of liquid in which the zeolite is crystallized. The liquid, in turn, must be treated for reuse or else be discarded, with potentially deleterious environmental consequences. Preparing commercially useful catalytic materials which contain the powdered zeolite also normally requires additional binding and forming steps. Typically, the zeolite powder as crystallized must be mixed with a binder material and then formed into shaped particles or agglomerates, using methods such as extruding, agglomeration, spray drying, and the like. These binding and forming steps greatly increase the complexity of catalyst manufacture involving zeolitic materials. The additional steps may also have an adverse effect on the catalytic performance of the zeolite so bound and formed.
D. Known Methods for Zeolites Having a Molar SiO.sub.2 /Al.sub.2 O.sub.3 Ratio Below 12
Prior art methods of preparing crystalline zeolites typically produce finely divided crystals which must be separated from an excess of liquid in which the zeolite is crystallized. The liquid, in turn, must be treated for reuse or else be discarded, with potentially deleterious environmental consequences. Preparing commercially useful catalytic materials which contain the powdered zeolite also normally requires additional binding and forming steps. Typically, the zeolite powder as crystallized must be mixed with a binder material and then formed into shaped particles or agglomerates, using methods such as extruding, agglomeration, spray drying, and the like. These binding and forming steps greatly increase the complexity of catalyst manufacture involving zeolitic materials. The additional steps may also have an adverse effect on the catalytic performance of the zeolite so bound and formed.
Crystalline zeolites may be divided into two general types based on crystal structure considerations. One type includes zeolites having a SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio in the crystalline lattice typically less than 12, which are conventionally prepared without an organic templating agent. Many of these zeolites also contain sodalite substructures, and have a tetrahedral atom density of less than about 15 TO.sub.2 /1000 [Angstrom].sup.3. Zeolites having these general characteristics include, for example, zeolites A, N-A, ZK-4, faujasite, X, Y, ZK-5 and rho.
A number of processes have been offered for preparing crystalline zeolites of this type within discrete particles. For example, Howell et al., in U.S. Pat. No. 3,119,660, teaches a method for producing crystalline metal aluminosilicate zeolite by reacting preformed bodies of clay particles in an aqueous reactant mixture including alkali metal oxide. Similar processes for preparing zeolites from formed bodies, which may contain zeolitic seed crystals, in alkali solutions are also taught in U.S. Pat. No. 4,424,144 to Pryor et al.; U.S. Pat. No. 4,235,753 to Brown et al.; U.S. Pat. No. 3,777,006 to Rundell et al.; U.S. Pat. No. 3,119,659 to Taggart et al.; U.S. Pat. No. 3,773,690 to Heinze et al.; U.S. Pat. No. 4,977,120 to Sakurada et al.; and GB 2 160 517 A. U.S. Pat. No. 3,094,383 teaches a method of forming an A type zeolite by aging a homogeneous reaction mixture out of contact with an external aqueous liquid phase but under conditions to prevent the dehydration of the mixture. GB 1 567 856 discloses a method of preparing zeolite A by heating an extruded mixture of metakaolin powder and sodium hydroxide.
In U.S. Pat. No. 4,058,586, Chi et al. disclose a method for crystallizing zeolites within formed particles containing added powdered zeolite, where the formed particles furnish all of the liquid needed for crystallization. Crystallizing the particles in an aqueous alkaline solution is not required using the process of Chi et al.
Verduijn, in WO 92/12928, teaches a method of preparing binder-free zeolite aggregates by aging silica-bound extruded zeolites in an aqueous ionic solution containing hydroxy ions. According to the disclosure of Verduijn, the presence of zeolite crystals in the extrudate is critical for making strong crystalline zeolite extrudates. Verduijn et al., in EPO A1/0,284,206, describe a method of preparing binderless zeolite L by forming silica and preferably 10-50 wt. % preformed zeolite L crystallites into particles, and then reacting the particles with an alkaline solution containing a source of alumina to form the zeolite L.
E. Known Methods for Zeolites Having a Molar SiO.sub.2 /Al.sub.2 O.sub.3 Ratio Above 12
More recently, similar methods have been proposed for preparing high silica zeolitic materials. Conventional methods for preparing high silica materials, having a SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio of greater than about 10, and more typically greater than about 20, typically involves crystallizing the zeolites from aqueous solution. For example, U.S. Pat. No. 3,702,886 to Argauer et al. teaches a method of preparing ZSM-5 from a solution containing tetrapropyl ammonium hydroxide, sodium oxide, an oxide of aluminum or gallium, an oxide of silica or germanium, and water. The digestion of the gel particles is carried out until crystals form. The crystals are separated from the liquid and recovered.
A variation of the preparation procedure involves using clay as a source of alumina in preparing high silica zeolites. For example, U.S. Pat. No. 4,091,007 discloses a method for preparing a crystalline aluminosilicate zeolite, specifically ZSM-4 or ZSM-5,from a reaction mixture where at least about 70 weight percent of the alumina is provided by an alumina-containing clay added to the reaction mixture. EPO A2/0,156,595 discloses the preparation of crystalline zeolites having a silica to alumina mole ratio greater than 12 and a Constraint Index of 1 to 12 by forming a mixture of seed crystals, a source of silica, a source of alumina and water into shaped particles, which are then crystallized in an aqueous reaction mixture containing a source of alkali cations. It is also taught that alumina-containing clay may be used as an alumina source. U.S. Pat. No. 4,522,705 is directed to a catalytic cracking catalyst comprising an additive prepared by the in-situ crystallization of a clay aggregate disclosed in EPO A2/0,156,595. U.S. Pat. No. 5,145,659 teaches methods for increasing the silica content of a zeolite supported on a matrix, where the matrix may be a clay.
Special methods for preparing the reaction mixture from which a zeolite may be crystallized have also been proposed. In U.S. Pat. No. 4,560,542, a dried hydrogel containing silica and alumina is contacted with a fluid medium containing an organic templating agent and maintained at specified crystallization conditions to form a crystalline aluminosilicate.
In U.S. Pat. No. 5,240,892, a reaction mixture containing at least about 30 weight percent solids content of alumina and precipitated silica is taught for preparing zeolites. The method of preparing the reaction mixture allows agitation of the mixture during crystallization, in spite of the high solids content of the mixture.
Zeolite crystallization from reaction mixtures initially containing a gel-like phase in equilibrium with an excess of liquid phase is disclosed in R. Aiello et al., "Zeolite Crystallization from Dense Systems", Materials Engineering 1992, Vol. 3, n. 3, pp. 407-416.
Other approaches to synthesis of crystalline zeolites have included preparing the zeolites in an essentially aqueous-free environment. These non-aqueous methods have been described, for example, in ZEOLITES, 1992, Vol. 12, Apr./May, p. 343; ZEOLITES 1990, Vol. 10, Nov./Dec., p. 753; ZEOLITES 1989, Vol. 9, November, p. 468; Nature, Vol. 317(12), September 1985, p. 157; and J. Chem. Soc., Chem. Commun., 1988, p. 1486. J. Chem. Soc., Chem. Commun., 1993, p. 659, describes a kneading method for synthesizing ZSM-35 in a non-aqueous system, in which the amount of liquids used to prepare a crystallization mixture is not sufficient to wet all the solid particles so that the conglomerate reactant is actually a mixture of dry powder and small doughy lumps.
F. U.S. Pat. No. 5,558,851
A method is disclosed in U.S. Pat. No. 5,558,851 (the '851 patent) for preparing a crystalline aluminosilicate zeolite from a reaction mixture containing only sufficient water so that the reaction mixture may be shaped if desired. In the method, the reaction mixture is heated at crystallization conditions and in the absence of an external liquid phase, so that excess liquid need not be removed from the crystallized material prior to drying the crystals. For zeolites having a SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio in the crystalline lattice greater than 12, there is no teaching of a method which does not require a template in the reaction mixture. Thus, the method of the '851 patent has the benefit of no external liquid phase to recycle or dispose, but still has the requirement for a template which can add greatly to the manufacturing expense of raw materials.
G. Zeolite ZSM-5
Zeolite ZSM-5 is a zeolite having a SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio in the crystalline lattice greater than 12, e.g., 20-5000. This zeolite is very useful in various hydrocarbon conversion processes, including dewaxing processes for lube oils. Zeolite ZSM-5 and the conventional preparation thereof are described in U.S. Pat. No. 3,702,886 (the '886 patent) and U.S. Pat. No. 3,770,614; and the disclosure of which, and particularly the methods of preparation and the templating agents used in the preparation, are incorporated herein by reference. The '886 patent teaches that a reaction mixture from which ZSM-5 can be suitably prepared is formed by mixing sources of silica and alumina with a templating agent, preferably tetrapropylammonium hydroxide, and sources of an alkali metal oxide, preferably sodium oxide. The teaching in the '851 patent for preparing a crystalline aluminosilicate zeolite from a reaction mixture containing only sufficient water so that the reaction mixture may be shaped if desired includes applying that method to Zeolite ZSM-5. However, for ZSM-5, there is no teaching of a method which does not require a template in the reaction mixture. Thus, for ZSM-5, the method of the '851 patent has the benefit of no external liquid phase to recycle or dispose, but still has the requirement for a template.
H. Deficiencies in Known Processes for Making ZSM-5
Some of the methods described above reduce the number of steps in crystallizing zeolites. However, for zeolites having a SiO.sub.2 /Al.sub.2 O.sub.3 molar ratio in the crystalline lattice greater that 12, especially ZSM-5, none of the cited patents provide a crystallization method combining a template-free reaction mixture with the ease of forming raw materials and a minimum of water into shaped particles, and crystallizing the zeolites within the shaped particles while eliminating an external liquid crystallization phase.
It would be advantageous to have a template-free, and thus relatively inexpensive, process for producing ZSM-5 crystalline zeolites not requiring an external liquid phase. This would greatly and beneficially reduce the cost of making such zeolites since such an external liquid phase is environmentally hazardous and must be treated or disposed of after the crystallization is complete. The method and process of the instant invention provides such a process for making ZSM-5.